US6649674B2 - Flame-proof polyester molding compositions comprising hydrotalcite, red phosphorus and melamine cyanurate - Google Patents

Flame-proof polyester molding compositions comprising hydrotalcite, red phosphorus and melamine cyanurate Download PDF

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US6649674B2
US6649674B2 US10/178,451 US17845102A US6649674B2 US 6649674 B2 US6649674 B2 US 6649674B2 US 17845102 A US17845102 A US 17845102A US 6649674 B2 US6649674 B2 US 6649674B2
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molding composition
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melamine
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US20030018108A1 (en
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Michael Wagner
Henricus Peerlings
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Lanxess Deutschland GmbH
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Bayer AG
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K2003/026Phosphorus

Definitions

  • the invention relates to flame-proof polyester molding compositions and more particularly to thin-walled moldings made therefrom.
  • a flame-proofed polyester molding composition is disclosed.
  • the composition that exhibits good flame-resistance, particularly in thin-walled moldings, contains red phosphorus, nitrogen-containing compounds and a small amount of a hydrotalcite.
  • the composition is particularly suitable for the preparation of moldings, sheeting and fibers.
  • Polyester molding compositions which are rendered flame-proof are of considerable importance in the electrical/electronics field and are used for the production of supports for voltage-carrying parts, for example. Apart from good flame-resistance, these compositions also have to have good mechanical and electrical properties. In addition, halogen-free molding compositions, particularly ones that are free of halogenated flame retarding agents, are increasingly being required.
  • JP-A 06-157880 describes molding compositions comprising polyethylene terephthalate which are made flame-resistant by melamine cyanurate and organophosphates and which exhibit good corrosion behavior in addition to good smoke fume properties.
  • Flame-proof polyester molding compositions are known from JP-A 11-140290 which contain fluorine compounds in addition to organophosphates and melamine cyanurate.
  • WO 98/30632 discloses flame-resistant thermoplastic polyesters which contain coated red phosphorus and a phenolic novolac resin.
  • WO 99/27016 describes red phosphorus in combination with an additional phosphorus compound and a fluoropolymer for the flame-proofing of mixtures of polybutylene terephthalate and polycarbonate.
  • JP-A 11-335531 relates to molding compositions comprising polybutylene and polyethylene terephthalate which in addition to coated red phosphorus contain triazine compounds and cyanuric acid compounds and a polyolefine, and which are suitable for use in the electrical/electronics field.
  • polyester molding compositions particularly polybutylene terephthalate, which comprise red phosphorus and melamine cyanurate
  • a hydrotalcite particularly in thin-walled components and moldings.
  • the molding compositions according to the invention exhibit an outstanding resistance in the glowing wire test.
  • the present invention thus relates to molding compositions containing:
  • Polyesters as defined by component A) firstly comprise polyalkylene terephthalates, i.e. reaction products of dicarboxylic acids, preferably aromatic dicarboxylic acids, or reactive derivatives thereof (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols, and mixtures of said reaction products, and secondly comprise completely aromatic polyesters which are described in detail below.
  • dicarboxylic acids preferably aromatic dicarboxylic acids, or reactive derivatives thereof (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols, and mixtures of said reaction products, and secondly comprise completely aromatic polyesters which are described in detail below.
  • Polyalkylene terephthalates may be produced by known methods from terephthalic acid (or reactive derivatives thereof) and aliphatic or cycloaliphatic diols containing 2 to 10 C atoms (Kunststoff-Handbuch, Volume VIII, pages 695 et seq., Karl-Hanser-Verlag, Kunststoff 1973).
  • the preferred polyalkylene terephthalates contain at least 80, preferably 90 mol % with respect to the dicarboxylic acid, of terephthalic acid radicals, and at least 80, preferably at least 90 mol % with respect to the diol component, of ethylene glycol and/or 1,3-propanediol and/or butanediol radicals.
  • the preferred polyalkylene terephthalates may contain up to 20 mol % of radicals of other aromatic dicarboxylic acids containing 8 to 14 C atoms, or of aliphatic dicarboxylic acids containing 4 to 12 C atoms, such as radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicar-boxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid or cyclohexane-diacetic acid.
  • the preferred polyalkylene terephthalates may contain up to 20 mol % of other aliphatic diols comprising 3 to 12 C atoms or cycloaliphatic diols comprising 6 to 21 C atoms, e.g.
  • the polyalkylene terephthalates may be branched by the incorporation of relatively small amounts of trihydric or tetrahydric alcohols or of tri- or tetrabasic carboxylic acids, such as those described in DE-A 19 00 270 and U.S. Pat. No. 3,692,744, incorporated herein by reference for example.
  • preferred branching agents include trimesic acid, trimellitic acid, trimethylol-ethane and -propane, and pentaerythritol.
  • Particularly preferred polyalkylene terephthalates are those which are produced solely from terephthalic acid and reactive derivatives thereof, (e.g. dialkyl esters thereof) and ethylene glycol and/or 1,3-propanediol and/or 1,4-butanediol (polyethylene-, polypropylene- and polybutylene terephthalates), as well as mixtures of these polyalkylene terephthalates.
  • the use of mixtures of polybutylene- and polyethylene terephthalates is quite particularly preferred.
  • the preferred polyalkylene terephthalates also include copolyesters which are produced from at least two of the aforementioned acid components and/or from at least two of the aforementioned alcohol components; the most preferred copolyesters are poly(ethylene glycol/1,4-butanediol) terephthalates.
  • the polyalkylene terephthalates generally have an intrinsic viscosity of about 0.4 to 1.5, preferably 0.5 to 1.3, as measured in phenol/o-dichlorobenzene (1:1 parts by weight) at 25° C.
  • the completely aromatic polyesters which are also suitable are the reaction products of aromatic dicarboxylic acids or reactive derivatives thereof with corresponding aromatic dihydroxy compounds.
  • the compounds discussed above in the description of the polyalkylene terephthalates may be used as aromatic dicarboxylic acids. Mixtures of 5 to 100 mol % isophthalic acid and 0 to 95 mol % terephthalic acid, particularly mixtures ranging from about 80% terephthalic acid to 20% isophthalic acid to approximately equivalent mixtures of these two acids, are preferred.
  • Z represents an alkylene or cycloalkylene group containing up to 8 carbon atoms, an arylene group containing up to 12 carbon atoms, a carbonyl group, an oxygen or a sulphur atom, a sulphonyl group or a chemical bond, and m has a value from 0 to 2.
  • These compounds may each comprise C 1 -C 6 alkyl or alkoxy groups as well as fluorine, chlorine or bromine as substituents on their phenylene units.
  • these substances include dihydroxyphenyl, di-(hydroxyphenyl)-alkanes, di-(hydroxypheny)cycloalkanes, di-(hydroxyphenyl) sulphide, di-(hydroxy-phenyl) ether, di-(hydroxyphenyl) ketone, di-(hydroxyphenyl) sulphoxide, di-(hydroxyphenyl), ⁇ , ⁇ -di(hydroxyphenyl)dialkylbenzenes, di-(hydroxy-phenyl)-sulphone, di-(hydroxybenzoyl)benzene, resorcinol and hydroquinone, as well as derivatives thereof which comprise alkylated or halogenated nuclei.
  • 2,2-di-(3′,5′-dimethyl-4′-hydroxyphenyl)propane, 2,2-di-(4′-hydroxy-phenyl-propane, 4,4′-dihydroxydiphenylsulphone, 2,2-di(3,5-di-chloro-dihydroxy-phenyl)propane, 1,1-di-(4′-hydroxyphenyl)cyclohexane and 3,4′-dihydroxybenzo-phenone are particularly preferred.
  • Mixtures of the aforementioned diol compounds may also be used.
  • any mixtures of these polyesters may be used, as may the polyesters cited below.
  • polyester is also to be understood to mean polycarbonates and polyester carbonates.
  • Polycarbonates and polyester carbonates are known from the literature or may be produced by methods known from the literature (for the production of poly-carbonates, for example, see Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964, as well as DE-A 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610 and DE-A 3 832 396; for the production of polyester carbonates, see DE-A 3 077 934, for example).
  • Aromatic polycarbonates may be produced, for example, by the reaction of diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzene-dicarboxylic acid dihalides, by the phase boundary method, optionally with the use of chain terminators, for example monophenols, and optionally with the use of trifunctional branching agents or branching agents with a functionality greater than three, e.g. triphenols or tetraphenols.
  • Diphenols for the production of aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of formula (II)
  • A denotes a single bond, a C 1 -C 5 alkylene, a C 2 -C 5 alkylidene, a C 5 -C 6 cyclo-alkylidene, —O—, —SO—, —CO—, —S— or a C 6 -C 12 arylene, on to which further aromatic rings, which optionally contain hetero atoms, may be condensed, or denotes a radical of formulae (III) or (IV)
  • B in each case denotes a C 1 -C 12 alkyl, preferably methyl, or a halogen, preferably chlorine and/or bromine,
  • x denotes 0, 1 or 2, which are each independent of each other
  • p denotes 1 or 0
  • R 1 and R 2 independently of each other and for each X 1 , denote hydrogen or a C 1 -C 6 alkyl, preferably hydrogen, methyl or ethyl,
  • X 1 denotes carbon
  • n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one X 1 atom R 1 and R 2 simultaneously denote an alkyl.
  • the preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C 1 -C 5 -alkanes, bis-(hydroxypbenyl)-C 5 -C 6 -cycloalkanes, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-sulphoxides, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulphones and ⁇ , ⁇ ′-bis-(hydroxyphenyl)-diisopropyl-benzenes, as well as derivatives thereof which comprise brominated and/or chlorinated nuclei.
  • diphenols include 4,4′-dihydroxydiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-dihydroxydiphenyl sulphide, 4,4′-dihydroxydiphenyl sulphone, as well as di- and tetrabrominated or chlorinated derivatives thereof, such as 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
  • 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularly preferred.
  • the diphenols may be used individually or in admixture.
  • Diphenols are known from the literature or may be obtained by methods known from the literature.
  • chain terminators which are suitable for the production of thermoplastic, aromatic polycarbonates include phenol, p-chlorophenol, p-tert-butylphenol and 2,4,6-tribromophenol, and also include long chain alkylphenols such as 4-(1,3-tetramethyl-butyl)-phenol according to DE-A 2 842 005 and monoalkylphenols or.
  • dialkylphenols which contain a total of 8 to 20 C atoms in their alkyl substituents, such as 3,5-di-tert.-butyl-phenol, p-iso-octylphenol, p-tert.-octylphenol, p-dodecyl-phenol, 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol.
  • the amount of chain terminators used is between 0.5 mol % and 10 mol % with respect to the molar sum of diphenols.
  • thermoplastic, aromatic polycarbonates have mean, weight average molecular weights (as measured by ultracentrifuging or by the measurement of scattered light, for example) ranging from 10,000 to 200,000, preferably 20,000 to 80,000.
  • thermoplastic aromatic polycarbonates may be branched in the known manner, preferably by the incorporation of 0.05 to 2.0 mol %, with respect to the sum of the diphenols used, of trifunctional compounds or of compounds with a functionality greater than three, for example those which contain three or more than three phenolic groups.
  • copolycarbonates Both homopolycarbonates and copolycarbonates are suitable.
  • 1 to 25% by weight, preferably 2.5 to 25% by weight, (with respect to the total amount of diphenols used) of polydiorganosiloxanes which comprise terminal hydroxy-aryloxy groups may also be used. These are known (see U.S. Pat. No. 3,419,634, for example) or may be prepared by methods known from the literature.
  • the production of copolycarbonates which contain polydiorganosiloxanes is described in DE-A 3 334 782, for example.
  • the preferred polycarbonates also include copolycarbonates of bisphenol A which comprise up to 15 mol %, with respect to the molar sum of diphenols, of diphenols other than those cited as being preferred or particularly preferred, especially 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane.
  • aromatic acid halides for the production of aromatic polyester carbonates include the diacid chlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4′-dicarboxylic acids and naphthalene-2,6-dicarboxylic acids.
  • Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20:1 are particularly preferred.
  • a carbonic acid halide preferably phosgene
  • phosgene may be used in addition as a derivative of a bifunctional acid.
  • suitable chain terminators for the production of aromatic polyester carbonates also include chlorocarbonic acid esters thereof, and acid chlorides of aromatic monocarboxylic acids which may optionally be substituted by C 1 -C 22 alkyl groups, as well as aliphatic C 2 -C 22 monocarboxylic acid chlorides.
  • the amount of chain terminators ranges from 0.1 to 10 mol % in each case, with respect to the moles of diphenols in the case of phenolic chain terminators, and with respect to the moles of dicarboxylic acid chlorides in the case of monocarboxylic acid chloride chain terminators.
  • the aromatic polyester carbonates may also contain hydroxycarboxylic acids as synthesis components.
  • the aromatic polyester carbonates may either be linear or branched in the known manner (in this respect, see DE-A 2 940 024 and DE-A 3 007 934 also).
  • branching agents which may be used include tri- or multifunctional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3′,4,4′-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-napthalene-tetra-carboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts from 0.01 to 1.0 mol % (with respect to the dicarboxylic acid dichlorides used), and tri- or multifunctional phenols such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxy-phenyl)-heptene-2,4,4-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-
  • the proportion of carbonate structural units may be arbitrarily varied.
  • the proportion of carbonate structural units is preferably up to 100 mol %, particularly up to 80 mol %, most preferably up to 50 mol %, with respect to the sum of ester groups and carbonate groups.
  • Both the ester- and the carbonate content of aromatic polyester carbonates may be present in the form of blocks or may be randomly distributed in the condensation polymer.
  • the relative solution viscosity ( ⁇ rel ) of the aromatic polycarbonates and polyester carbonates falls within the range from 1.18 to 1.4, preferably 1.22 to 1.3 (as measured on solutions of 0.5 g polycarbonate or polyester carbonate in 100 ml methylene chloride solution at 25° C.).
  • thermoplastic aromatic polycarbonates and polyester carbonates may be used alone or in any mixture with each other.
  • polyester block copolymers may be used, such as those described in U.S. Pat. No. 3,651,014.
  • component B) is a mixture of red phosphorus b1) and a nitrogen compound b2) in an amount of 5 to 30 parts by weights, preferably 10 to 20 parts by weight with respect to the total molding composition. It has been found, particularly for polybutylene terephthalate, that particularly good results may be obtained by using 14 to 20 parts by weight of a mixture of red phosphorus b1) and nitrogen compound b2).
  • Red phosphorus as defined by component b1) is to be understood to mean all colored allotropic forms of phosphorus in finely divided form.
  • the average particle size of the particles thereof usually ranges between 0.1 and 100 ⁇ m, preferably between 0.2 and 50 ⁇ m.
  • the particle size of the phosphorus may be adjusted by grinding, particularly by wet-grinding in ball mills or bead mills. Suitable grinding media include water and organic solvents such as toluene, mineral oil, dimethylformamide, di-methylacetamide and formic acid.
  • red phosphorus which is treated or encapsulated in a known manner may also preferably be used.
  • Suitable materials for coating red phosphorus include inorganic materials such as metal hydroxides or silicates, organic compounds, preferably polymers such as phenol-formaldehyde resins, urea-melamine-phenol-formaldehyde resins, urea-resorcinol-formaldehyde-hexamethylenetetramine resins, epoxy resins or formaldehyde-silicate resins, and mixtures of inorganic and organic coating agents. The latter mixtures may be deposited on red phosphorus simultaneously or in successive steps.
  • red phosphorus which has been treated with organic polymers has proved particularly useful.
  • the compounds which are used are preferably formaldehyde resins, with resorcinol-urea-formaldehyde resins being particularly preferred.
  • red phosphorus examples include products from Clariant, such as, for example, Red Phosphorus SFD, Exolit RP 602, Exolit RP 605 or Exolit RP 689, Exolit RP 690, Exolit RP 694 and Exolit RP 695, the latter four products being concentrates of red phosphorus in polymeric carrier materials.
  • Clariant such as, for example, Red Phosphorus SFD, Exolit RP 602, Exolit RP 605 or Exolit RP 689, Exolit RP 690, Exolit RP 694 and Exolit RP 695, the latter four products being concentrates of red phosphorus in polymeric carrier materials.
  • the nitrogen compound b2) which is used in addition to red phosphorus may be melamine, melamine cyanurate, -oxalate, -phosphate prim., -phosphate sec. or -pyro-phosphate sec., neopentyl glycol boric acid melamine, or melamine phosphate. Guanidine salts and related compounds are also suitable.
  • Melamine cyanurate is particularly preferred within the scope of the present invention. Melamine cyanurate is to be understood to be the reaction product formed from what are preferably equimolar amounts of melamine and cyanuric acid.
  • Suitable melamine cyanurate is commercially available, for example, as Melapur® MC 25 (supplied by DSM Melapur, Heerlen, Holland) or Budit® 315 (supplied by Budenheim, Budenheim, Germany).
  • the melamine cyanurate may also be treated with known inorganic and/or organic media.
  • the average particle size of this material usually ranges between 0.1 and 25 ⁇ m, average particle diameters from 0.1 to 10 ⁇ m being preferred and average particle diameters from 0.1 to 5 ⁇ m being particularly preferred.
  • a hydrotalcite as defined by component C) is to be understood to be a synthetic or natural mineral of general formula
  • M 2+ denotes a divalent metal ion, preferably Mg 2+ ,
  • M 3+ denotes a trivalent metal ion, preferably Al 3+ ,
  • a n denotes an n-valent anion, preferably CO 3 2 ⁇ or SO 4 2 ⁇ ,
  • n denotes an integer greater than 0, preferably 2,
  • x denotes 0 to 0.5, preferably 0 to 0.33
  • the compound of composition (Mg 6 (CO 3 )[Al(OH) 6 ] 2 (OH) 4 4H 2 O) is particularly preferred.
  • Hydrotalcites may be obtained commercially under the trade names Hysafe® 539, Nacid®, Sorbplus® PM or Talcid®.
  • hydrotalcites which are used may optionally be modified by appropriate chemical treatment.
  • the molding composition contains, as component D), 1 to 50 parts by weight, preferably 10 to 40 parts by weight, most preferably 10 to 35 parts by weight, of added fillers and/or reinforcing agents.
  • Fibrous or particulate fillers and reinforcing agents which may be added include glass fibers, glass beads, glass mats, carbon fibers, aramid fibers, potassium titanate fibers, natural fibers, amorphous hydrated silicas, magnesium carbonate, barium sulphate, mica, silicates, quartz, French chalk, kaolin, titanium dioxide, wollastonite, etc. These substances may also be surface-treated.
  • the preferred reinforcing agents are commercially available glass fibers. These glass fibers, which generally have a fiber diameter between 8 and 18 ⁇ m, may be added as continuous fibers or as cut or chopped glass fibers, wherein the fibers may be coated with a suitable size system and with a bonding agent or bonding agent system, e.g. a silane-based system.
  • acicular mineral fillers are also suitable.
  • acicular mineral fillers are to be understood as mineral fillers with a strongly pronounced acicular character.
  • Acicular wollastonite is an example thereof.
  • the mineral preferably has an L/D (length/diameter) ratio of 8:1 to 35:1, preferably 8:1 to 11:1.
  • the mineral filler may optionally be surface-treated.
  • the molding compositions according to the invention may also contain further conventional functional additives as component E.
  • the latter are most generally copolymers which are preferably synthesised from at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile or esters of acrylic or methacrylic acid which contain 1 to 18 C atoms in their alcohol component.
  • additives examples include thermal stabilizers, anti-thermal crosslinking agents, UV-stabilizers, plasticizers, flow enhancers and processing aids and anti-drip agents, wherein fluorine-containing compounds such as poly-tetrafluoroethylene (e.g. Teflon®) are particularly preferred, flame-retardant agents, internal lubricants and mold release agents, nucleating agents, anti-static agents and stabilisers, as well as colorants and pigments.
  • fluorine-containing compounds such as poly-tetrafluoroethylene (e.g. Teflon®) are particularly preferred, flame-retardant agents, internal lubricants and mold release agents, nucleating agents, anti-static agents and stabilisers, as well as colorants and pigments.
  • Additives in the form of organic and inorganic compounds of metals may also be included. These include oxides and sulphides of zinc, oxides and hydroxides of magnesium, copper oxide, iron oxide, metal carbonates such as calcium or magnesium carbonate, and borates, particularly zinc borates, as well as generally stoichiometric mixtures of metal compounds.
  • plastics molding compositions were produced by compounding the components given in Table 1.
  • the individual components were mixed in a double-shaft extruder (ZSK 45 supplied by Haake, 20 cm worm length) at temperatures between 260 and 300° C., were discharged as a strand, cooled until they could be granulated, and granulated. Drying (generally for two days at 70° C. in a vacuum drying oven) was followed by processing the granular material at temperatures between 260 and 300° C. to form standard test specimens for UL94V testing, and also to form test specimens for the glowing wire test according to IEC DIN 695-2-1, by means of which the burning properties of the molding compositions according to the invention were determined.
  • hydrotalcite Hydrotalcite (Hysafe® 539, 3.;. Huber Corp., Havre de Grace, USA)
  • the flame-resistance of plastics is determined by Method UL94V (in this respect, see a) Underwriters Laboratories Inc. Standard of Safety, “Test for Flammability of Plastic Materials for Parts in Devices and Appliances”, page 14 et seq., Northbrook 1998; b) J. Troitzsch, “International Plastics Flammability Handbook”, page 346 et seq., Hanser Verlag, Kunststoff 1990), which is extensively used in the electrical/-electronics field. Using this method, the after-burn times and drip-off behavior of ASTM standard test specimens are determined.
  • Classification UL94V-1 requires that the individual after-burn times are no longer than 30 seconds and that the sum of the after-burn times after 10 ignitions of 5 specimens is no greater than 250 seconds. The total after-glow time must not be longer than 250 seconds. The remaining criteria are identical to those mentioned above. A material is given a fire classification of UL94V-2 if it exhibits burning drip-off behavior but fulfils all the other criteria of classification UL94V-1.
  • Another test of the flame-resistance of plastics is the glowing wire test according to DIN IEC 695-2-1.
  • 10 test specimens for example panels of geometry 60 ⁇ 60 ⁇ 2 mm or 1 mm
  • a glowing wire at temperatures between 550 and 960° C., for the maximum temperature at which an after-burn time of 30 seconds is not exceeded and the specimen does not exhibit burning drip-off behavior.
  • This test is also of particular interest in the electrical/electronics field, since, in the event of fire or in cases of overload, components in electronic products can reach temperatures such that parts in their immediate vicinity can ignite. Conditions of thermal loading such as these are reproduced in the glowing wire test.
  • Table 1 shows the results of the compounding experiments performed (data given in parts by weight):

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US10/178,451 2001-06-27 2002-06-24 Flame-proof polyester molding compositions comprising hydrotalcite, red phosphorus and melamine cyanurate Expired - Fee Related US6649674B2 (en)

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DE10130831.0 2001-06-27
DE10130831 2001-06-27
DE10130831A DE10130831A1 (de) 2001-06-27 2001-06-27 Flammfeste Polyesterformmassen mit Hydrotalcit, rotem Phosphor und Melamincyanurat

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US20060183835A1 (en) * 2004-08-12 2006-08-17 Clariant Gmbh Flame-retardant polymers with glow-wire resistance
US20080075983A1 (en) * 2006-09-25 2008-03-27 Ming-Ming Chen Flame-retardant filament and method of manufacture thereof and protective sleeves constructed therefrom
US8604105B2 (en) 2010-09-03 2013-12-10 Eastman Chemical Company Flame retardant copolyester compositions

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US20060183835A1 (en) * 2004-08-12 2006-08-17 Clariant Gmbh Flame-retardant polymers with glow-wire resistance
US20080075983A1 (en) * 2006-09-25 2008-03-27 Ming-Ming Chen Flame-retardant filament and method of manufacture thereof and protective sleeves constructed therefrom
US8604105B2 (en) 2010-09-03 2013-12-10 Eastman Chemical Company Flame retardant copolyester compositions
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DE10130831A1 (de) 2003-01-16
JP2004530784A (ja) 2004-10-07
BR0210669A (pt) 2004-10-05
MXPA03011396A (es) 2004-07-01
CN1216094C (zh) 2005-08-24
KR20040024567A (ko) 2004-03-20
CN1522278A (zh) 2004-08-18

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